CN116535998A - 一种热熔复合石材玻璃耐热eva胶片的制备方法 - Google Patents
一种热熔复合石材玻璃耐热eva胶片的制备方法 Download PDFInfo
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Abstract
本发明公开了一种热熔复合石材玻璃耐热EVA胶片的制备方法,本发明属于EVA夹层胶技术领域,采用EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂、其他助剂共混造粒挤出流延成膜,采用硅胶吸酸剂对EVA胶膜分解释放的醋酸分子进行吸收,防止腐蚀石材的同时,抑制EVA脱酸分解,提高EVA胶膜的耐热性能,辅以甲基乙烯基聚硅氧烷或甲基乙烯基MQ硅树脂,抑制主链热降解,稳定自由基有作用,抑制侧基氧化,能改善胶膜的力学强度,热氧化稳定性得到提高,本发明的公开的制备方法,简便易行,利用硅胶吸酸剂与硅树脂共混改性不会明显降低胶膜强度,有效降低了醋酸的生成,减少醋酸腐蚀石材,从而延长热熔复合石材玻璃的使用寿命。
Description
技术领域
本发明属于EVA夹层胶技术领域,具体涉及一种热熔复合石材玻璃耐热EVA胶片的制备方法。
背景技术
透光石玻璃又称热熔复合石材玻璃,是一种将天然石材进行薄片加工打磨成型后,采用高分子材料胶片与玻璃合片,经过高温、高压复合而成的拥有天然石材纹理又具备钢化玻璃物理性能的建筑材料。石材薄片可以选择各种常用的天然石材如:大理石、花岗岩、等,厚度一般为3-5mm,可以应用于建筑幕墙、室外景观、吧台、屏风隔断、吊顶隔墙、发光地面等。例如,安徽报业大厦、海宁图书馆等地标建筑均采用此种建材形成独特的装饰风格。陈冀渝报道了热熔复合石材玻璃兼有天然石材装饰性和玻璃透光性的功能,用于建筑物能收到特有的使用效果。透光石玻璃具有高强度、抗紫外线、良好的耐候性、优越的隔声性能,与玻璃深加工成镀膜中空玻璃后将具备普通节能玻璃的所有性能。在兼顾性能的同时,还能呈现石材的天然纹理,透光不透视,夜间配合灯光亮化,能够产生独特的光影效果。白天可展现天然石材的独特纹理和质感,夜间通过室内灯光也能显现更加细腻的石材纹理脉络。透光石玻璃因石材薄片的存在将大量的紫外线阻挡在外,透光不透视,可以让部分可见光进入室内,光线柔和、温馨。透光石玻璃的石材是不具备透光性能的,知识为了兼顾天然石材纹理效果和玻璃防水性能,应用在建筑室内外装修中。正因为石材薄片不透光,导致玻璃与石材薄片中间的夹胶膜承受更多的温热。此外,通常,紫外线、湿度和热量等环境因素作用下,透光石玻璃内的EVA会产生酸,并且这种酸会使腐蚀天然石材薄片,从而导致石材薄片本身的变色、污渍等劣化问题。是一款适用于严酷湿热环境和高标准户用环境组件中的高端产品。而且由于EVA是线性高分子共聚物,因而其耐热性及内聚强度等较差,这些都限制了其在热熔复合石材玻璃的应用范围,EVA胶膜制造的透光石玻璃在太阳下受热变软、延伸,导致透光石玻璃变形。热熔复合石材玻璃作为新型的绿色建材,可综合利用各种资源,是替代天然石材的高档装饰品,能有效地抑制对天然石材的过度开采,可以推动环境保护,循环经济和低碳经济的发展。对于要求胶接强度更高的类型,普通的EVA甚至醋酸乙烯含量较大的EVA仍不能满足使用要求。中国专利CN109337596A公开了一种EVA导热复合胶膜的制备方法,利用的是选取纳米片状氧化铝、纳米片状氮化硼为主要导热填料,但胶膜并不透明,氧化铝、氮化硼纳米片由于较大的表面能容易团聚不易分散均匀,而高含量填料的团聚会造成胶膜内部出现孔洞和孔隙,而且透光石玻璃并不需要导热,本领域技术人员亟待开发出一种热熔复合石材玻璃耐热EVA胶片的制备方法以满足现有的应用市场和性能需求。
发明内容
有鉴于此,本发明提供一种热熔复合石材玻璃耐热EVA胶片的制备方法。
一种热熔复合石材玻璃耐热EVA胶片的制备方法,包括以下步骤:第一步、将EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂、其他助剂按配比混合均匀,在双螺杆挤出机中进行挤出、造粒,得到EVA胶片粒料;第二步、将上述得到的EVA胶片粒料,55~70℃干燥2~4h后,在EVA胶片生产线挤出流延淋膜经缠绕收卷后,即得。
进一步的,所述催化剂为过氧化二异丙苯、过氧化苯甲酸特丁酯、过氧化苯甲酰、过氧化叔丁酸2-乙基己酯、过氧化十二酰中的其中一种或多种。
进一步的,所述第一步EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂、其他助剂的质量比为77~85∶17~21∶5~7∶11~13∶0.1~0.4。
进一步的,所述硅树脂为甲基乙烯基聚硅氧烷或甲基乙烯基MQ硅树脂中的一种或多种。
EVA在热的情况下脱醋酸,产生双键,由此产生活泼的烯丙基氢,使得EVA耐热性差,热老化是由于在高温区域产生的脱醋酸反应和热氧化反应所引起的,特别是脱醋酸反应,又能继续引起热解脱反应,结果使醋酸与双键产生反应;通过实践中观察发现,EVA这种脱醋酸的耐热性差现象还具有的传染性,胶片还会从邻近胶片吸收醋酸进而引起耐热性差;
进一步的,其中双螺杆挤出机各段的温度参数设置为160℃、165℃、170℃、175℃、180℃、180℃,螺杆转速65~70r/min,喂料速度9~10r/min。
以往EVA胶膜有持续的酸释放特性,即便是在正常使用过程中,仍然会有酸释放和脱层等失效现象。特别是EVA胶膜分解释放的醋酸分子,不仅会腐蚀玻璃和石材,导致热熔复合石材玻璃的长期可靠性风险增加。
以往,吸酸剂是一种性能稳定剂,用于氟橡胶的加工,为金属氧化物、氢氧化物,如氧化镁、氧化锌、氧化铅、氧化钙、氢氧化钙等,并不是本领域常规使用原料。
硅胶也并不是常用的吸酸剂,EVA胶膜以往也并不使用吸酸剂。
进一步的,所述硅胶吸酸剂为ELASTOSIL E 91或ELASTOSIL E 92 N中的其中一种。
进一步的,所述其他助剂为抗氧剂,抗氧剂包括受阻酚类抗氧剂或磷酸酯类抗氧剂中一种或几种。
稳定性明显好于纯EVA胶膜。这是因为改性的EVA胶膜加入了乙烯基硅树脂,高温时发生了交联,形成集中交联网络,当受到外力作用或热降解时,只有少数交联键断裂,不会明显降低胶膜强度。因此,乙烯基硅树脂不仅能改善胶膜的机械强度,而且能提高其热稳定性。
本发明的有益效果:
本发明公开的热熔复合石材玻璃耐热EVA胶片的制备方法,采用EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂、其他助剂共混造粒挤出流延成膜,采用硅胶吸酸剂对EVA胶膜分解释放的醋酸分子进行吸收,防止腐蚀石材的同时,抑制EVA脱酸分解,提高EVA胶膜的耐热性能,同时硅胶吸酸剂为ELASTOSIL E 91或ELASTOSIL E 92 N具有流动性,易加工,吸收EVA的同时发生交联,辅以甲基乙烯基聚硅氧烷或甲基乙烯基MQ硅树脂,抑制主链热降解外,对自由基有稳定作用,抑制侧基的氧化,能改善胶膜的力学强度,在主链和硅氧链上形成位阻,使主链较难成环降解,热氧化稳定性得到提高,同时,硅树脂形成的交联结构也在一定程度上阻碍主链成环,进而提高EVA胶膜的耐热性。
本发明相比现有技术具有如下优点:
相比于现有技术中,采用导热填料等复杂方法提高EVA胶膜的耐热性,透光石玻璃内的EVA会产生酸,并且这种酸会使腐蚀天然石材薄片,从而导致石材薄片本身的变色、污渍等劣化问题。本发明的公开的制备方法,简便易行,利用硅胶吸酸剂与硅树脂共混改性不会明显降低胶膜强度,在一定条件下的交联,使EVA从原来的线形热塑性高分子变为交联的三维网状热固性分子,针对性地进行了EVA胶膜的酸吸收和耐热改性,有效降低了醋酸的生成,减少醋酸腐蚀石材,从而延长热熔复合石材玻璃的使用寿命。
具体实施方式
实施例1
硅树脂为乙烯基含量4%的嘉兴联化UC252甲基乙烯基聚硅氧烷、硅胶吸酸剂ELASTOSIL E 91。石材为3mm广厦新材MS917薄石片。
热熔复合石材玻璃耐热EVA胶片的制备方法,包括以下步骤:硅树脂为甲基乙烯基聚硅氧烷或甲基乙烯基MQ硅树脂,第一步、将EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂、其他助剂抗氧剂1010按配比混合均匀,EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂过氧化二异丙苯、抗氧剂1010的质量比为77∶17∶5∶11∶0.1,在双螺杆挤出机中进行挤出、造粒,得到EVA胶片粒料,双螺杆挤出机各段的温度参数设置为160℃、165℃、170℃、175℃、180℃、180℃,螺杆转速65r/min,喂料速9r/min;第二步、将上述得到的EVA胶片粒料,70℃干燥4h后,在EVA胶片生产线挤出流延淋膜经缠绕收卷后,即得。
产品性能:胶膜厚度0.2mm,透光率91.5%,交联度88.5%,热熔复合石材玻璃石材-玻剥离强度65.6N/cm,120kW·h/m2紫外老化后剥离强度35.5N/cm,DH1000高温高湿老化后剥离强度38.5N/cm;软化点105℃、热稳定性无颜色转黑或焦状物产生(180℃×24h)、77.8硬度(邵尔A)、扯断强度17.8MPa、断裂伸长率465.4%,TD收缩率0.50%,纵向收缩率2.54%。
实施例2
石材为瑞赫姆YPX-07黑石薄片。RH-S0836甲基乙烯基MQ硅树脂润禾乙烯基含量2%,硅胶吸酸剂ELASTOSILE 92 N。
热熔复合石材玻璃耐热EVA胶片的制备方法,包括以下步骤:硅树脂为甲基乙烯基MQ硅树脂,第一步、将EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂、其他助剂抗氧剂1076按配比混合均匀,EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂过氧化二异丙苯、其抗氧剂1076的质量比为80∶181∶6∶12∶0.3,在双螺杆挤出机中进行挤出、造粒,得到EVA胶片粒料,双螺杆挤出机各段的温度参数设置为160℃、165℃、170℃、175℃、180℃、180℃,螺杆转速68r/min,喂料速度9r/min;第二步、将上述得到的EVA胶片粒料,60℃干燥3h后,在EVA胶片生产线挤出流延淋膜经缠绕收卷后,即得。
产品性能:胶膜厚度0.2mm,透光率91.7%,交联度88.5%,热熔复合石材玻璃石材-玻剥离强度63.5N/cm,120kW·h/m2紫外老化后剥离强度36.7N/cm,DH1000高温高湿老化后剥离强度38.7N/cm;软化点105℃、热稳定性无颜色转黑或焦状物产生(180℃×24h)、78.0硬度(邵尔A)、扯断强度17.6MPa、断裂伸长率472.2%,TD收缩率0.51%,纵向收缩率2.52%。
实施例3
石材为兴雁XY360443mm大理石薄板,XJY-8206甲基乙烯基MQ硅树脂江西新嘉懿新材料有限公司乙烯基含量4%,硅胶吸酸剂ELASTOSIL E 91。
热熔复合石材玻璃耐热EVA胶片的制备方法,包括以下步骤:硅树脂为甲基乙烯基聚硅氧烷,第一步、将EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂、其他助剂抗氧剂Revonox608按配比混合均匀,EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂过氧化二异丙苯、其他助剂的质量比为85∶21∶7∶13∶0.4,在双螺杆挤出机中进行挤出、造粒,得到EVA胶片粒料,双螺杆挤出机各段的温度参数设置为160℃、165℃、170℃、175℃、180℃、180℃,螺杆转速70r/min,喂料速度10r/min;第二步、将上述得到的EVA胶片粒料,70℃干燥4h后,在EVA胶片生产线挤出流延淋膜经缠绕收卷后,即得。
产品性能:胶膜厚度0.2mm,透光率91.4%,交联度88.4%,热熔复合石材玻璃石材-玻剥离强度63.7N/cm,120kW·h/m2紫外老化后剥离强度37.6N/cm,DH1000高温高湿老化后剥离强度38.4N/cm;软化点105℃、热稳定性无颜色转黑或焦状物产生(180℃×24h)、77.8硬度(邵尔A)、扯断强度15.4MPa、断裂伸长率469.8%,TD收缩率0.53%,纵向收缩率2.51%。
实施例4
硅树脂为甲基乙烯基MQ硅树脂江西新嘉懿新材料有限公司乙烯基含量4%,硅胶吸酸剂ELASTOSIL E 92 N,石材为超悦石材公司4mm啡钻花岗岩薄板。
热熔复合石材玻璃耐热EVA胶片的制备方法,包括以下步骤:硅树脂为甲基乙烯基MQ硅树脂,第一步、将EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂、其他助剂抗氧剂242按配比混合均匀,EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂过氧化二异丙苯、其他助剂的质量比为83∶19∶6∶12∶0.3,在双螺杆挤出机中进行挤出、造粒,得到EVA胶片粒料,双螺杆挤出机各段的温度参数设置为160℃、165℃、170℃、175℃、180℃、180℃,螺杆转速68r/min,喂料速度10r/min,所述其他助剂为抗氧剂242和抗氧剂1010的重量比例为1:1的混合物;第二步、将上述得到的EVA胶片粒料,60℃干燥3h后,在EVA胶片生产线挤出流延淋膜经缠绕收卷后,即得。
产品性能:胶膜厚度0.2mm,透光率91.7%,交联度88.9%,热熔复合石材玻璃石材-玻剥离强度64.1N/cm,120kW·h/m2紫外老化后剥离强度39.5N/cm,DH1000高温高湿老化后剥离强度36.3N/cm;软化点105℃、热稳定性无颜色转黑或焦状物产生(180℃×24h)、77.6硬度(邵尔A)、扯断强度16.3MPa、断裂伸长率456.7%,TD收缩率0.52%,纵向收缩率2.56%。
将实施例1~4的胶片生产线挤出流延淋膜工艺如表1所示:
表1实施例1~4的的EVA胶片生产线挤出流延淋膜工艺参数
注:检测参考HG/T5377-2018乙烯-醋酸乙烯酯(EVA)胶膜。
Claims (7)
1.一种热熔复合石材玻璃耐热EVA胶片的制备方法,其特征在于,包括以下步骤:第一步、将EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂、其他助剂按配比混合均匀,在双螺杆挤出机中进行挤出、造粒,得到EVA胶片粒料;第二步、将上述得到的EVA胶片粒料,55~70℃干燥2~4h后,在EVA胶片生产线挤出流延淋膜经缠绕收卷后,即得。
2.根据权利要求1所述的热熔复合石材玻璃耐热EVA胶片的制备方法,其特征在于,所述催化剂为过氧化二异丙苯、过氧化苯甲酸特丁酯、过氧化苯甲酰、过氧化叔丁酸2-乙基己酯、过氧化十二酰中的其中一种或多种。
3.根据权利要求1所述的热熔复合石材玻璃耐热EVA胶片的制备方法,其特征在于,所述第一步EVA颗粒、硅胶吸酸剂、有机硅树脂、催化剂、其他助剂的质量比为77~85∶17~21∶5~7∶11~13∶0.1~0.4。
4.根据权利要求1所述的热熔复合石材玻璃耐热EVA胶片的制备方法,其特征在于,所述硅树脂为甲基乙烯基聚硅氧烷或甲基乙烯基MQ硅树脂中的一种或多种。
5.根据权利要求1所述的热熔复合石材玻璃耐热EVA胶片的制备方法,其特征在于,其中双螺杆挤出机各段的温度参数设置为160℃、165℃、170℃、175℃、180℃、180℃,螺杆转速65~70r/min,喂料速度9~10r/min。
6.根据权利要求1所述的热熔复合石材玻璃耐热EVA胶片的制备方法,其特征在于,所述硅胶吸酸剂为ELASTOSIL E 91或ELASTOSIL E 92 N中的其中一种。
7.根据权利要求1所述的热熔复合石材玻璃耐热EVA胶片的制备方法,其特征在于,所述其他助剂为抗氧剂,抗氧剂包括受阻酚类抗氧剂或磷酸酯类抗氧剂中一种或几种。
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